Solvent-free bio-based emulsion

ABSTRACT

A process comprising:
         contacting at least one bio-based amorphous polyester resin with an optional plasticizer to form a pre-blend mixture;   neutralizing the pre-blend mixture with a neutralizing agent;   contacting the pre-blend mixture with a surfactant;   melt-mixing the pre-blend mixture;   contacting the melt-mixed mixture with de-ionized water to form an oil in water emulsion possessing a latex; and   recovering the latex.

This application is a divisional of copending application Ser. No.12/967,370, filed Dec. 13, 2010, the disclosure of the copendingapplication being totally incorporated herein by reference. Also, thefiling date or priority date of Dec. 14, 2010 for the copendingapplication Ser. No. 12/967,370 is hereby claimed for the common subjectmatter contained in the present continuation application.

TECHNICAL FIELD

The present disclosure relates to processes for producing resinemulsions useful in producing toners. More specifically, solvent-freeprocesses are provided for the production of bio-based polyester resinsutilizing extruders.

BACKGROUND

Numerous processes are within the purview of those skilled in the artfor the preparation of toners. Emulsion aggregation (EA) is one suchmethod. Emulsion aggregation toners may be used in formingelectrophotographic images. Emulsion aggregation techniques may involvethe formation of a polymer emulsion by heating a monomer and undertakingbatch or semi-continuous emulsion polymerization, as disclosed in, forexample, U.S. Pat. No. 5,853,943, the disclosure of which is herebyincorporated by reference in its entirety. Emulsionaggregation/coalescing processes for the preparation of toners areillustrated in a number of patents, such as U.S. Pat. Nos. 5,290,654,5,278,020, 5,308,734, 5,344,738, 6,593,049, 6,743,559, 6,756,176,6,830,860, 7,029,817, and 7,329,476, and U.S. Patent ApplicationPublication Nos. 2006/0216626, 2008/0107989, 2008/0107990, 2008/0236446,and 2009/0047593. The disclosures of each of the foregoing patents arehereby incorporated by reference in their entirety.

Polyester EA ultra low melt (ULM) toners have been prepared utilizingamorphous and crystalline polyester resins as illustrated, for example,in U.S. Patent Application Publication No. 2008/0153027, the disclosureof which is hereby incorporated by reference in its entirety.

The incorporation of these polyesters into the toner requires that theyfirst be formulated into emulsions prepared by solvent containing batchprocesses, for example solvent flash emulsification and/or solvent-basedphase inversion emulsification (PIE), which are both time andenergy-consuming. In both cases, large amounts of organic solvents, suchas ethyl acetate, ketones or alcohols, have been used to dissolve theresins, which may require subsequent energy intensive distillation toform the latexes, and are not environmentally friendly.

Solventless latex emulsions have been formed in either a batch orextrusion process through the addition of a neutralizing solution, asurfactant solution and water to a thermally softened resin asillustrated, for example, in U.S. Patent Application Publications SerialNos. 2009/0246680 and 2009/0208864, the disclosures of each of which arehereby incorporated by reference in their entirety.

Improved processes for the preparation of polymer latexes suitable foruse in a toner remain desirable.

SUMMARY

The present disclosure provides processes for producing toners, andtoners produced thereby. In embodiments, a process of the presentdisclosure includes contacting at least one bio-based amorphouspolyester resin with an optional plasticizer to form a pre-blendmixture; neutralizing the pre-blend mixture with a neutralizing agent;contacting the pre-blend mixture with a surfactant; melt-mixing thepre-blend mixture; contacting the melt-mixed mixture with de-ionizedwater to form an oil in water emulsion possessing a latex; andrecovering the latex.

In other embodiments, a process of the present disclosure includescontacting at least one bio-based amorphous polyester resin derived atleast in part from a material such as natural triglyceride vegetableoils, phenolic plant oils, and combinations thereof, with an optionalplasticizer in a first section of an extruder to form a resin mixture;neutralizing the resin mixture in a second section of the extruder witha neutralizing agent such as ammonium hydroxide, potassium hydroxide,sodium hydroxide, sodium carbonate, sodium bicarbonate, lithiumhydroxide, potassium carbonate, potassium bicarbonate, piperazine,tris-hydroxymethyl-aminomethane, and combinations thereof; contactingthe resin mixture with a surfactant in the extruder; melt-mixing theresin mixture in the extruder; contacting the melt-mixed mixture withde-ionized water to form an oil in water emulsion possessing a latex inthe extruder; and recovering the latex from the extruder.

In yet other embodiments, a process of the present disclosure includescontacting at least one bio-based polyester resin including componentssuch as a fatty dimer diol, a fatty dimer diacid, D-isosorbide,L-tyrosine, glutamic acid, and combinations thereof, with an optionalcrystalline resin and an optional plasticizer in an extruder to form aresin mixture; neutralizing the resin mixture in the extruder with aneutralizing agent; contacting the resin mixture in the extruder with asurfactant; melt-mixing the resin mixture in the extruder; contactingthe melt-mixed mixture with de-ionized water in the extruder to form anoil in water emulsion possessing a latex; recovering the latex from theextruder; contacting the latex with an optional crystalline resin, anoptional colorant, and an optional wax to form a second mixture;aggregating the mixture to form particles; adjusting the pH of themixture to from about 3 to about 10 to stop growth of the particles;coalescing the particles at a pH from about 5 to about 8 to form tonerparticles; and recovering the toner particles.

BRIEF DESCRIPTION OF DRAWINGS

Various embodiments of the present disclosure will be described hereinbelow with reference to the figures wherein:

FIG. 1 is a schematic diagram of an extruder for preparation of abio-based resin latex according to embodiments of the presentdisclosure;

FIG. 2 is a graph showing the particle size distribution of an emulsionformed in Example 1 of the present disclosure;

FIG. 3 is a graph showing the particle size distribution of an emulsionformed in Example 2 of the present disclosure;

FIG. 4 is a graph showing the particle size distribution of an emulsionformed in Example 3 of the present disclosure; and

FIG. 5 is a graph showing the particle size distribution of an emulsionformed in Example 4 of the present disclosure.

DETAILED DESCRIPTION

To make an EA toner, conventional processes using bio-based resinsinclude first converting the resin into an aqueous dispersion (latex).However the bio-resin is only soluble in toxic organic solvents, such asdichloromethane, and can only be emulsified via a solvent flash processwith the use of surfactant as a stabilizer at lab scale. However, thesolvent flash emulsification process utilizes a 10 to 1 ratio of solventto resin, with a low batch yield of less than 15% solid content. In thesolvent removal process, a large amount of solvent needs to beevaporated at the end of the emulsification, which takes a long time tocomplete. Furthermore, the use of toxic organic solvent is anenvironmental concern, and the solvent process may not be applied at aproduction scale.

The present disclosure provides a new formulation and process for theemulsification of bio-based resins to form nano-scale particlesdispersed in water (latex) without the use of organic solvents by anextrusion process. Bio-based products, as used herein, in embodiments,include commercial and/or industrial products (other than food or feed)that may be composed, in whole or in significant part, of biologicalproducts or renewable domestic agricultural materials (including plant,animal, or marine materials) and/or forestry materials as defined by theU.S. Office of the Federal Environmental Executive.

As noted above, the latex of the present disclosure and the process forits production are solvent free and, therefore, there are no traces ofsolvent present in the latex, as none are used for their production. Theresulting emulsion may then be used for forming a toner, paint, powder,coating, compounding additive for pharmaceuticals, encapsulant for adrug, adhesive, or food additive. In embodiments, the process forproducing the emulsion may be a continuous process.

In embodiments, a process of the present disclosure, which emulsifies abio-resin into latex, includes the following: blending the bio-resinwith a surfactant (such as sodium dodecylbenzene sulfonate (SDBS),sodium lauryl sulfate (SLS), or combinations thereof, and a neutralizersuch as sodium hydroxide (NaOH), piperazine, or combinations thereof, toform a mixture; melt mixing the above mixture in an extruder;emulsifying the melt mixture by injecting de-ionized water into theextruder; and diluting the mixture with de-ionized water.

The desired properties of the bio-emulsion (particle size and solidscontent) can be achieved by adjusting the concentration of thesurfactant and neutralizer. The quality of the emulsion can be affectedby process parameters such as extruder speed, material feed rate,extruder temperature profile, and injection nozzle position.

The process of the present disclosure may be continuous, therebyenhancing the efficiency of the process.

Resins

Any resin may be utilized in forming a latex emulsion of the presentdisclosure. In embodiments, the resins may be an amorphous resin, acrystalline resin, and/or a combination thereof. In further embodiments,the resin may be a polyester resin, including the resins described inU.S. Pat. Nos. 6,593,049 and 6,756,176, the disclosures of each of whichare hereby incorporated by reference in their entirety. Suitable resinsmay also include a mixture of an amorphous polyester resin and acrystalline polyester resin as described in U.S. Pat. No. 6,830,860, thedisclosure of which is hereby incorporated by reference in its entirety.

In embodiments, the resin may be a polyester resin formed by reacting adiol with a diacid in the presence of an optional catalyst. For forminga crystalline polyester, suitable organic diols include aliphatic diolswith from about 2 to about 36 carbon atoms, such as 1,2-ethanediol,1,3-propanediol, 1,4-butanediol, 1,5-pentanediol,2,2-dimethylpropane-1,3-diol, 1,6-hexanediol, 1,7-heptanediol,1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, andthe like, including their structural isomers. The aliphatic diol may be,for example, utilized in an amount of from about 40 to about 60 molepercent, in embodiments from about 42 to about 55 mole percent, inembodiments from about 45 to about 53 mole percent, and a second diolcan be utilized in an amount of from about 0 to about 10 mole percent,in embodiments from about 1 to about 4 mole percent of the resin.

Examples of organic diacids or diesters including vinyl diacids or vinyldiesters selected for the preparation of the crystalline resins includeoxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid,azelaic acid, sebacic acid, fumaric acid, dimethyl fumarate, dimethylitaconate, cis, 1,4-diacetoxy-2-butene, diethyl fumarate, diethylmaleate, phthalic acid, isophthalic acid, terephthalic acid,naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid,cyclohexane dicarboxylic acid, malonic acid and mesaconic acid, adiester or anhydride thereof. The organic diacid may be utilized in anamount of, for example, in embodiments from about 40 to about 60 molepercent, in embodiments from about 42 to about 52 mole percent, inembodiments from about 45 to about 50 mole percent, and a second diacidcan be utilized in an amount of from about 0 to about 10 mole percent ofthe resin.

Examples of crystalline resins include polyesters, polyamides,polyimides, polyolefins, polyethylene, polybutylene, polyisobutyrate,ethylene-propylene copolymers, ethylene-vinyl acetate copolymers,polypropylene, mixtures thereof, and the like. Specific crystallineresins may be polyester based, such as poly(ethylene-adipate),polypropylene-adipate), poly(butylene-adipate), poly(pentylene-adipate),poly(hexylene-adipate), poly(octylene-adipate),poly(ethylene-succinate), polypropylene-succinate),poly(butylene-succinate), poly(pentylene-succinate),poly(hexylene-succinate), poly(octylene-succinate),poly(ethylene-sebacate), poly(propylene-sebacate),poly(butylene-sebacate), poly(pentylene-sebacate),poly(hexylene-sebacate), poly(octylene-sebacate),poly(decylene-sebacate), poly(decylene-decanoate),poly(ethylene-decanoate), poly(ethylene dodecanoate),poly(nonylene-sebacate), poly(nonylene-decanoate),copoly(ethylene-fumarate)-copoly(ethylene-sebacate),copoly(ethylene-fumarate)-copoly(ethylene-decanoate),copoly(ethylene-fumarate)-copoly(ethylene-dodecanoate),copoly(2,2-dimethylpropane-1,3-diol-decanoate)-copoly(nonylene-decanoate),poly(octylene-adipate). Examples of polyamides includepoly(ethylene-adipamide), poly(propylene-adipamide),poly(butylenes-adipamide), poly(pentylene-adipamide),poly(hexylene-adipamide), poly(octylene-adipamide),poly(ethylene-succinimide), and poly(propylene-sebecamide). Examples ofpolyimides include poly(ethylene-adipimide), poly(propylene-adipimide),poly(butylene-adipimide), poly(pentylene-adipimide),poly(hexylene-adipimide), poly(octylene-adipimide),poly(ethylene-succinimide), poly(propylene-succinimide), andpoly(butylene-succinimide).

The crystalline resin may be present, for example, in an amount of fromabout 1 to about 50 percent by weight of the toner components, inembodiments from about 5 to about 35 percent by weight of the tonercomponents. The crystalline resin can possess various melting points of,for example, from about 30° C. to about 120° C., in embodiments fromabout 50° C. to about 90° C. The crystalline resin may have a numberaverage molecular weight (M_(n)), as measured by gel permeationchromatography (GPC) of, for example, from about 1,000 to about 50,000,in embodiments from about 2,000 to about 25,000, and a weight averagemolecular weight (M_(w)) of, for example, from about 2,000 to about100,000, in embodiments from about 3,000 to about 80,000, as determinedby Gel Permeation Chromatography using polystyrene standards. Themolecular weight distribution (M_(w)/M_(n)) of the crystalline resin maybe, for example, from about 2 to about 6, in embodiments from about 3 toabout 4.

Polycondensation catalysts which may be utilized in forming thecrystalline polyesters include tetraalkyl titanates, dialkyltin oxidessuch as dibutyltin oxide, tetraalkyltins such as dibutyltin dilaurate,and dialkyltin oxide hydroxides such as butyltin oxide hydroxide,aluminum alkoxides, alkyl zinc, dialkyl zinc, zinc oxide, stannousoxide, or combinations thereof. Such catalysts may be utilized inamounts of, for example, from about 0.01 mole percent to about 5 molepercent based on the starting diacid or diester used to generate thepolyester resin.

Suitable crystalline resins which may be utilized, optionally incombination with an amorphous resin as described below, include thosedisclosed in U.S. Patent Application Publication No. 2006/0222991, thedisclosure of which is hereby incorporated by reference in its entirety.In embodiments, a suitable crystalline resin may include a resin formedof ethylene glycol and a mixture of dodecanedioic acid and fumaric acidco-monomers with the following formula:

wherein b is from about 5 to about 2000 and d is from about 5 to about2000. In embodiments, a suitable crystalline resin may include a resinformed from dodecanedioic acid and 1,9-nonanediol monomers.

In embodiments, resins utilized in accordance with the presentdisclosure may also include bio-based amorphous resins. As used herein,a bio-based resin is a resin or resin formulation derived from abiological source such as vegetable oil instead of petrochemicals. Asrenewable polymers with low environmental impact, their principaladvantages are that they reduce reliance on finite resources ofpetrochemicals; they sequester carbon from the atmosphere. A bio-resinincludes, in embodiments, for example, a resin wherein at least aportion of the resin is derived from a natural biological material, suchas animal, plant, combinations thereof, and the like. In embodiments, atleast a portion of the resin may be derived from materials such asnatural triglyceride vegetable oils (e.g. rapeseed oil, soybean oil,sunflower oil) or phenolic plant oils such as cashew nut shell liquid(CNSL), combinations thereof, and the like. Suitable bio-based amorphousresins include polyesters, polyamides, polyimides, polyisobutyrates, andpolyolefins, combinations thereof, and the like. In some embodiments,the bio-based resins are also biodegradable.

Examples of amorphous bio-based polymeric resins which may be utilizedinclude polyesters derived from monomers including a fatty dimer diacidor diol of soya oil, D-isosorbide, and/or amino acids such as L-tyrosineand glutamic acid as described in U.S. Pat. Nos. 5,959,066, 6,025,061,6,063,464, and 6,107,447, and U.S. Patent Application Publication Nos.2008/0145775 and 2007/0015075, the disclosures of each of which arehereby incorporated by reference in their entirety. Combinations of theforegoing may be utilized, in embodiments. Suitable amorphous bio-basedresins include those commercially available from Advanced ImageResources, under the trade name BIOREZ™ 13062, BIOREZ™ 15062, andBIOREZ™ AIR-64-116. In embodiments, a suitable amorphous bio-basedpolymeric resin which may be utilized may include a dimer diacid of soyaoil, isosorbide (which may be obtained from corn starch), with theremainder of the amorphous bio-based polymeric resin being1,4-cyclohexane dicarboxylic acid (CHDA) and/or dimethyl terephthalate(DMT). In embodiments the bio-based polymeric resin may includeisosorbide and 1,4-cyclohexane dicarboxylic acid.

In embodiments, a suitable amorphous bio-based resin may have a glasstransition temperature of from about 45° C. to about 70° C., inembodiments from about 50° C. to about 65° C., a weight averagemolecular weight (Mw) of from about 2,000 to about 200,000, inembodiments of from about 5,000 to about 100,000, a number averagemolecular weight (Mn) as measured by gel permeation chromatography (GPC)of from about 1,000 to about 10,000, in embodiments from about 2,000 toabout 8,000, a molecular weight distribution (Mw/Mn) of from about 2 toabout 20, in embodiments from about 3 to about 15, and a viscosity atabout 130° C. of from about 10 Pa*S to about 100000 Pa*S, in embodimentsfrom about 50 Pa*S to about 10000 Pa*S.

The amorphous bio-based resin may be present, for example, in amounts offrom about 1 to about 95 percent by weight of the toner components, inembodiments from about 5 to about 50 percent by weight of the tonercomponents, although the amount of the amorphous bio-based resin can beoutside of these ranges.

In embodiments, the amorphous bio-based polyester resin may have aparticle size of from about 50 nm to about 500 nm in diameter, inembodiments from about 75 nm to 300 nm in diameter.

In embodiments, suitable latex resin particles may include one or moreof the crystalline resins described above, and one or more amorphousbio-based resins, such as a BIOREZ™ resin described herein.

One, two, or more resins may be used. In embodiments, where two or moreresins are used, the resins may be in any suitable ratio (e.g., weightratio) such as for instance of from about 1% (first resin)/99% (secondresin) to about 99% (first resin)/1% (second resin), in embodiments fromabout 4% (first resin)/96% (second resin) to about 96% (first resin)/4%(second resin), although weight ratios outside these ranges may beutilized. Where the core resin includes a crystalline resin, a bio-basedamorphous resin, and another amorphous resin, the weight ratio of thethree resins may be from about 98% (amorphous resin): 1% (crystallineresin): 1% (bio-based amorphous resin), to about 0% (amorphous resin):15% (crystalline resin): 85% (bio-based amorphous resin).

In embodiments, the resin may be formed by condensation polymerizationmethods. In other embodiments, the resin may be formed by emulsionpolymerization methods.

Plasticizer

In embodiments, a plasticizer may be added to the resins describedabove. The plasticizer may be used to soften the resin to a viscositysuitable for passage through an extruder. The softened resin may besufficiently viscous so as to not be free-flowing at room temperature,but sufficiently pliable to be mixed by the extruder. The complexviscosity of the softened resin, sometimes referred to herein, inembodiments, as a pre-blend mixture, may be from about 10 Pa*S to about1,000 Pa*S at about 130° C., in embodiments, from about 50 Pa*S to about500 Pa*S. The complex viscosity of the resin pre-blend mixture can bemeasured using any suitable rheometer. For example, a 25 mm sample disccan be prepared by molding about 0.5 grams of pre-blend mixture under apressure of about 10,000 lbs and the complex viscosity response atvarious temperature and shear rates can be determined using a parallelplate rheometer such as a Rheometric Scientific Corporation Model ARES.

In embodiments, waxes may be used as plasticizers for softening theresin. The wax may be provided in a wax dispersion, which may include asingle type of wax or a mixture of two or more different waxes. Whenincluded, the wax may be present in an amount of, for example, fromabout 1% by weight to about 25% by weight of the resin, in embodimentsfrom about 5% by weight to about 20% by weight of the resin.

Waxes that may be utilized include waxes having, for example, a weightaverage molecular weight of from about 500 to about 20,000, inembodiments from about 1,000 to about 10,000. Suitable plasticizer waxesinclude ester waxes obtained from higher fatty acid and higher alcohol,such as stearyl stearate and behenyl behenate; ester waxes obtained fromhigher fatty acid and monovalent or multivalent lower alcohols, such asbutyl stearate, propyl oleate, glyceride monostearate, glyceridedistearate, and pentaerythritol tetra behenate; ester waxes obtainedfrom higher fatty acid and multivalent alcohol multimers, such asdiethyleneglycol monostearate, dipropyleneglycol distearate, diglyceryldistearate, and triglyceryl tetrastearate; sorbitan higher fatty acidester waxes, such as sorbitan monostearate, and cholesterol higher fattyacid ester waxes, such as cholesteryl stearate. Other suitableplasticizer waxes include functionalized waxes having amines, amides,for example AQUA SUPERSLIP 6550™, SUPERSLIP 6530™ available from MicroPowder Inc., fluorinated waxes, for example POLYFLUO 190™, POLYFLUO200™, POLYSILK 19™, POLYSILK 14™ available from Micro Powder Inc., mixedfluorinated and amide waxes, such as aliphatic polar amidefunctionalized waxes; aliphatic waxes including esters of hydroxylatedunsaturated fatty acids, for example MICROSPERSION 19™ available fromMicro Powder Inc., imides, esters, quaternary amines, carboxylic acidsor acrylic polymer emulsions, for example JONCRYL 74™, 89™, 130™, 537™,and 538™, all available from SC Johnson Wax, and chlorinatedpolypropylenes and polyethylenes, available from Allied Chemical,Petrolite Corporation, and/or SC Johnson wax. Mixtures and combinationsof the foregoing waxes may also be used in embodiments.

In embodiments, if the polyester resin is a bio-based amorphous resin, acrystalline polyester resin may be used as a plasticizer, which lowersthe softening temperature of the amorphous resin such that, attemperatures near the boiling point of water, the viscosity of the meltmix is low enough to form an emulsion.

Neutralizing Agent

In embodiments, the resin may be pre-blended with a weak base orneutralizing agent. In embodiments the base may be contacted with theresin as a solid or in an aqueous solution. The resin and theneutralizing agent may be simultaneously fed through a co-feedingprocess, which may accurately control the feed rate of both the base andthe resin into the extruder throughout the process, and which may thenbe melt-mixed followed by emulsification. Utilizing this process allowsfor control of the base concentration and a more efficient process.Co-feeding may allow for process repeatability and stability, and lowerinitial start-up waste.

In embodiments, the neutralizing agent may be used to neutralize acidgroups in the resins, so a neutralizing agent herein may also bereferred to as a “basic neutralization agent.” Any suitable basicneutralization reagent may be used in accordance with the presentdisclosure. In embodiments, suitable basic neutralization agents mayinclude both inorganic basic agents and organic basic agents. Suitablebasic agents may include ammonium hydroxide, potassium hydroxide, sodiumhydroxide, sodium carbonate, sodium bicarbonate, lithium hydroxide,potassium carbonate, potassium bicarbonate, combinations thereof, andthe like. Suitable basic agents may also include monocyclic compoundsand polycyclic compounds having at least one nitrogen atom, such as, forexample, secondary amines, which include aziridines, azetidines,piperazines, piperidines, pyridines, bipyridines, terpyridines,dihydropyridines, morpholines, N-alkylmorpholines,1,4-diazabicyclo[2.2.2]octanes, 1,8-diazabicycloundecanes,1,8-diazabicycloundecenes, dimethylated pentylamines, trimethylatedpentylamines, pyrimidines, pyrroles, pyrrolidines, pyrrolidinones,indoles, indolines, indanones, benzindazones, imidazoles,benzimidazoles, imidazolones, imidazolines, oxazoles, isoxazoles,oxazolines, oxadiazoles, thiadiazoles, carbazoles, quinolines,isoquinolines, naphthyridines, triazines, triazoles, tetrazoles,pyrazoles, pyrazolines, and combinations thereof. In embodiments, themonocyclic and polycyclic compounds may be unsubstituted or substitutedat any carbon position on the ring. Other basic agents used as aneutralizer include, for example, tris-hydroxymethyl-aminomethane.

The basic agent may be utilized as a solid such as, for example, sodiumhydroxide flakes, so that it is present in an amount of from about0.001% by weight to 50% by weight of the resin, in embodiments fromabout 0.01% by weight to about 25% by weight of the resin, inembodiments from about 0.1% by weight to 5% by weight of the resin.

As noted above, the basic neutralization agent may be added to a resinpossessing acid groups. The addition of the basic neutralization agentmay thus raise the pH of an emulsion including a resin possessing acidgroups to a pH of from about 5 to about 12, in embodiments, from about 6to about 11. The neutralization of the acid groups may, in embodiments,enhance formation of the emulsion.

Surfactants

In embodiments, the process of the present disclosure may include addinga surfactant, before or during the melt-mixing, to the resin at anelevated temperature. In embodiments, a solid surfactant may be co-fedwith the resin and the neutralizing agent into the extruder. Inembodiments, a solid surfactant may be added to the resin and theneutralizing agent to form a pre-blend mixture prior to melt-mixing.Where utilized, a resin emulsion may include one, two, or moresurfactants. The surfactants may be selected from ionic surfactants andnonionic surfactants. Anionic surfactants and cationic surfactants areencompassed by the term “ionic surfactants.” In embodiments, thesurfactant may be added as a solid or as a solution with a concentrationof from about 5% to about 100% (pure surfactant) by weight, inembodiments, from about 10% to about 95% by weight. In embodiments, thesurfactant may be utilized so that it is present in an amount of fromabout 0.01% to about 20% by weight of the resin, in embodiments, fromabout 0.1% to about 16% by weight of the resin, in embodiments, fromabout 1% to about 14% by weight of the resin.

Anionic surfactants which may be utilized include sulfates andsulfonates, sodium dodecylsulfate (SDS), sodium dodecylbenzene sulfonate(SDBS), sodium lauryl sulfate (SLS), sodium dodecylnaphthalene sulfate,dialkyl benzenealkyl sulfates and sulfonates, acids such as abitic acidavailable from Aldrich, NEOGEN R™, NEOGEN SC™ obtained from DaiichiKogyo Seiyaku, combinations thereof, and the like. Other suitableanionic surfactants include, in embodiments, DOWFAX™ 2A1, analkyldiphenyloxide disulfonate from The Dow Chemical Company, and/orTAYCA POWER BN2060 from Tayca Corporation (Japan), which are branchedsodium dodecylbenzene sulfonates (SDBS). Combinations of thesesurfactants and any of the foregoing anionic surfactants may be utilizedin embodiments.

Examples of the cationic surfactants, which are usually positivelycharged, include, for example, alkylbenzyl dimethyl ammonium chloride,dialkyl benzenealkyl ammonium chloride, lauryl trimethyl ammoniumchloride, alkylbenzyl methyl ammonium chloride, alkyl benzyl dimethylammonium bromide, benzalkonium chloride, cetyl pyridinium bromide, C₁₂,C₁₅, C₁₇ trimethyl ammonium bromides, halide salts of quaternizedpolyoxyethylalkylamines, dodecylbenzyl triethyl ammonium chloride,MIRAPOL™ and ALKAQUAT™, available from Alkaril Chemical Company,SANIZOL™ (benzalkonium chloride), available from Kao Chemicals, and thelike, and mixtures thereof.

Examples of nonionic surfactants that may be utilized for the processesillustrated herein include, for example, polyvinyl alcohol, polyacrylicacid, methalose, methyl cellulose, ethyl cellulose, propyl cellulose,hydroxy ethyl cellulose, carboxy methyl cellulose, polyoxyethylene cetylether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether,polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether,polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether,polyoxyethylene nonylphenyl ether, dialkylphenoxypoly(ethyleneoxy)ethanol, available from Rhone-Poulenc as IGEPALCA-210™, IGEPAL CA-520™, IGEPAL CA-720™, IGEPAL CO-890™, IGEPAL CO-720™,IGEPAL CO-290™, IGEPAL CA-210™, ANTAROX 890™ and ANTAROX 897™. Otherexamples of suitable nonionic surfactants may include a block copolymerof polyethylene oxide and polypropylene oxide, including thosecommercially available as SYNPERONIC PE/F, in embodiments SYNPERONICPE/F 108. Combinations of these surfactants and any of the foregoingsurfactants may be utilized in embodiments.

Resin Mixture Processing

As noted above, the present process includes melt-mixing a mixture in anextruder at an elevated temperature containing a bio-based resin, anoptional plasticizer, a solid or aqueous surfactant, and a neutralizingagent. The elevated temperature may be from about 30° C. to about 200°C., in embodiments from about 50° C. to about 150° C., in embodimentsfrom about 70° C. to about 100° C. In embodiments, the process of thepresent disclosure may be continuous.

Turning to FIG. 1, melt-mixing of the resin may be conducted in anextruder 30, which may be a twin screw extruder, a kneader such as aHaake mixer, a batch reactor, or any other device capable of intimatelymixing viscous materials to create near homogenous mixtures. Stirring,although not necessary, may be utilized to enhance formation of thelatex. Any suitable stirring device may be utilized. In embodiments, thestirring may be at from about 10 revolutions per minute (rpm) to about5,000 rpm, in embodiments from about 20 rpm to about 2,000 rpm, inembodiments from about 50 rpm to about 1,000 rpm. The stirring need notbe at a constant speed and may be varied. For example, as the heating ofthe mixture becomes more uniform, the stirring rate may be increased.

More than one resin may be utilized in forming the latex. As notedabove, the resin may be a bio-based amorphous resin, a crystallineresin, or a combination thereof. In embodiments, the resin may be anamorphous resin and the elevated temperature may be a temperature abovethe glass transition temperature of the amorphous resin. In embodiments,the resin may be a crystalline resin and the elevated temperature may bea temperature above the melting point of the crystalline resin. Infurther embodiments, the resin may be a mixture of amorphous andcrystalline resins and the temperature may be above the glass transitiontemperature of the mixture.

In embodiments, the resin, the plasticizer and the neutralizing agentmay be pre-blended prior to melt-mixing. In embodiments, the resin andthe plasticizer may be mixed in a tumbler 10 for from about 10 minutesto about 60 minutes, in embodiments from about 15 minutes to about 30minutes, at a rotor speed of from about 1 rotation per minute (rpm) toabout 20 rpm, in embodiments from about 5 rpm to about 15 rpm, toprepare a pre-blend mixture.

The pre-blend resin mixture is fed through a screw feeder 20 coupled tothe extruder 30. The pre-blend resin mixture may be co-fed into theextruder 30 with a neutralizing agent in solid form, such as flakes orpellets being fed through a separate feeder (not shown). If theneutralizing agent is used in an aqueous solution, the dissolvedneutralizing agent may be pre-mixed with the surfactant and water in avessel 45 and co-fed through pump 55 to extruder injection port 75 orfed separately to injection port 75. The neutralizing agent may be fedat a rate such that it is at a concentration of about 0.2% by weight toabout 5% by weight of the resin, in embodiments, from about 0.4% byweight to about 2% by weight of the resin. Concentration of thecomponents is provided rather than the rates to achieve the desiredcomposition, since flow and feed rates vary with the scale of theprocessing equipment (e.g., extruder 30).

In embodiments, a solid surfactant may be utilized and co-fed with theresin into the extruder feed hopper. The surfactant may be added to theresin composition before, during, or after melt-mixing and before,during, or after the addition of the neutralizing agent. Alternatively,the surfactant may be in an aqueous solution. More specifically, as thepre-blend resin mixture travels down the extruder 30, a solution of thesurfactant may be fed into the extruder's injection port 75, from thevessel 45 via the diaphragm pump 55 and heated via heat exchanger 65. Ifa solid neutralizing agent is utilized, the water in the surfactantsolution activates the neutralizing agent while the surfactant ismelt-mixed with the resin to produce a homogeneous mixture of aneutralized resin. The surfactant is fed at a rate such that it is at aconcentration of from about 0.5% by weight to about 20% by weight of theresin, in embodiments, from about 2% by weight to about 15% by weight ofthe resin.

In embodiments, a plasticizer may be injected directly into the extruder30 to blend the resin and the plasticizer within the extruder 30, thuseliminating the need for pre-blending. The plasticizer may be fedthrough an extruder injection port 70, from a vessel 40 via a diaphragmpump 50 and heated via heat exchanger 60. The plasticizer may beinjected at a rate such that it is at a concentration of about 1% byweight to about 100% by weight of the resin, in embodiments, from about10% by weight to about 50% by weight of the resin. The injection port 70may be disposed at a first section I of the extruder 30, which acts as amelting zone, prior to the injection port 75, which supplies thesurfactant solution. The injection port 75 may be disposed at a secondsection II subsequent to the first section, such that the surfactant isadded to the mixture after the plasticizer has been mixed with the resinin the extruder 30. In embodiments, the injection ports 70 and 75 may bedisposed at the same section, e.g., first section, in the extruder 30such that the plasticizer and surfactant are fed simultaneously.

Emulsion Formation

Once the resin, plasticizer, neutralizing agent and surfactant aremelt-mixed, the resulting dispersion mixture may be contacted with waterto form an oil in water latex emulsion. For example, de-ionized water(DIW) may be added to form a latex with a solids content of from about5% to about 50%, in embodiments, of from about 10% to about 40%. Inembodiments, water temperatures may be from about 20° C. to about 110°C., in embodiments, from about 60° C. to about 100° C.

Contact between the water and the resin mixture may be achieved viawater injection ports into the extruder. As shown in FIG. 1, as themelt-mixed resin mixture travels down the extruder 30, pre-heated, DIWmay be added at three subsequent ports 110, 140, and 170 at section IIIof the extruder 30. DIW may be stored in a tank 80 and be fed to theextruder's injection ports 110, 140, and 170 via diaphragm pumps 90,120, and 150. The DIW is heated via heat exchangers 100, 130, and 160,respectively.

Addition of water is advantageous so that the formation of an oil inwater emulsion may be gradual, ensuring that the materials continue tomix rather than phase separate, and to optimize emulsion formation inthe extruder. In embodiments, the ports may inject preheated de-ionizedwater into the extruder at rates of from about 1 g/min to about 400g/min, in embodiments, of from about 5 g/min to about 200 g/min, suchthat the final solids content of the latex is from about 10% to about40%, in embodiments, from about 15% to about 35%.

The product exiting from the extruder may include a stream of latex thatis collected in a steam traced tank 200 with gentle agitation withadditional DIW fed from tank 80 to achieve the desired final productsolids content, via diaphragm pump 180 and heated via heat exchanger190. Once a desired latex is achieved, the latex is discharged as alatex stream 210 for storage and later use in theaggregation/coalescence process described below.

The particle size of the latex emulsion formed can be controlled by theconcentration ratio of plasticizer, surfactant and/or neutralizing agentto polyester resin. The solids concentration of the latex may becontrolled by the ratio of the resin mixture to water.

In accordance with the present disclosure, it has been found that theprocesses herein may produce emulsified bio-based resin particles.

The emulsified resin particles in the aqueous medium may have a size ofabout 1500 nm or less, such as from about 10 nm to about 1200 nm, inembodiments from about 30 nm to about 1,000 nm. Particle sizedistribution of a latex of the present disclosure may be from about 60nm to about 300 nm, in embodiments, from about 125 nm to about 250 nm.The coarse content of the latex of the present disclosure may be fromabout 0% by weight to about 1% by weight, in embodiments, from about0.1% by weight to about 0.5% by weight. The solids content of the latexof the present disclosure may be from about 5% by weight to about 75% byweight, in embodiments, from about 30% by weight to about 50% by weight.

Following emulsification, additional surfactant, water, and/orneutralizing agent may optionally be added to dilute the emulsion,although this is not required. Following emulsification, the emulsionmay be cooled to room temperature, for example from about 20° C. toabout 25° C.

Various benefits may be obtained utilizing the processes of the presentdisclosure. For example, the process, formulation, and materialdisclosed herein: is a solvent free latex derived from a bio-based resinwith no traces of solvent; creates a new class of bio based emulsionswith a wide range of applications in the marking material field as wellas in many coatings, food, pharmaceutical applications (paints, films,food products, drug packaging) where bio-based and solvent free latexesare desired; is produced in an environmentally and commerciallyattractive (cost effective) and scaleable process; and is the only knownmethod of creating a latex in an environmentally friendly way fromcertain bio-based resins.

In embodiments, the latex emulsions of the present disclosure may beutilized to produce toners.

Toner

Once the resin mixture has been contacted with water to form an emulsionas described above, the resulting bio-based resin latex may then beutilized to form a toner by any method within the purview of thoseskilled in the art. The bio-based latex emulsion may be contacted with acolorant, optionally in a dispersion, and other additives to form anultra low melt toner by a suitable process, in embodiments, an emulsionaggregation and coalescence process.

In embodiments, the optional additional ingredients of a tonercomposition, including additional resins, such as crystalline resins,colorant, wax, and other additives, may also be added before, during orafter melt-mixing the resin to form the latex emulsion of the presentdisclosure. The additional ingredients may be added before, during orafter formation of the latex emulsion. In further embodiments, thecolorant may be added before the addition of the surfactant.

Colorants

As the colorant to be added, various known suitable colorants, such asdyes, pigments, mixtures of dyes, mixtures of pigments, mixtures of dyesand pigments, and the like, may be included in the toner. The colorantmay be added in amounts from about 0.1 to about 35 weight percent of thetoner, in embodiments from about 1 to about 15 weight percent of thetoner, in embodiments from about 3 to about 10 weight percent of thetoner.

As examples of suitable colorants, mention may be made of carbon blacklike REGAL 330®; magnetites, such as Mobay magnetites MO8029™, MO8060™;Columbian magnetites; MAPICO BLACKS™ and surface treated magnetites;Pfizer magnetites CB4799™, CB5300™, CB5600™, MCX6369™; Bayer magnetites,BAYFERROX 8600™, 8610™; Northern Pigments magnetites, NP-604™, NP-608™;Magnox magnetites TMB-100™, or TMB-104™; and the like. As coloredpigments, there can be selected cyan, magenta, yellow, red, green,brown, blue or mixtures thereof. Generally, cyan, magenta, or yellowpigments or dyes, or mixtures thereof, are used. The pigment or pigmentsare generally used as water based pigment dispersions.

Specific examples of pigments include SUNSPERSE 6000, FLEXIVERSE andAQUATONE water based pigment dispersions from SUN Chemicals, HELIOGENBLUE L6900™, D6840™, D7080™, D7020™, PYLAM OIL BLUE™, PYLAM OIL YELLOW™,PIGMENT BLUE 1™ available from Paul Uhlich & Company, Inc., PIGMENTVIOLET 1™, PIGMENT RED 48™, LEMON CHROME YELLOW DCC 1026™, E.D.TOLUIDINE RED™ and BON RED C™ available from Dominion Color Corporation,Ltd., Toronto, Ontario, NOVAPERM YELLOW FGL™, HOSTAPERM PINK E™ fromHoechst, and CINQUASIA MAGENTA™ available from E.I. DuPont de Nemours &Company, and the like. Generally, colorants that can be selected areblack, cyan, magenta, or yellow, and mixtures thereof. Examples ofmagentas are 2,9-dimethyl-substituted quinacridone and anthraquinone dyeidentified in the Color Index as CI-60710, CI Dispersed Red 15, diazodye identified in the Color Index as CI-26050, CI Solvent Red 19, andthe like. Illustrative examples of cyans include copper tetra(octadecylsulfonamido) phthalocyanine, x-copper phthalocyanine pigment listed inthe Color Index as CI 74160, CI Pigment Blue, Pigment Blue 15:3, andAnthrathrene Blue, identified in the Color Index as CI-69810, SpecialBlue X-2137, and the like. Illustrative examples of yellows arediarylide yellow 3,3-dichlorobenzidene acetoacetanilides, a monoazopigment identified in the Color Index as CI-12700, CI Solvent Yellow 16,a nitrophenyl amine sulfonamide identified in the Color Index as ForonYellow SE/GLN, CI Dispersed Yellow 33 2,5-dimethoxy-4-sulfonanilidephenylazo-4′-chloro-2,5-dimethoxy acetoacetanilide, and Permanent YellowFGL. Colored magnetites, such as mixtures of MAPICO BLACK™, and cyancomponents may also be selected as colorants. Other known colorants canbe selected, such as Levanyl Black A-SF (Miles, Bayer) and SunsperseCarbon Black LHD 9303 (Sun Chemicals), and colored dyes such as NeopenBlue (BASF), Sudan Blue OS (BASF), PV Fast Blue B2G01 (AmericanHoechst), Sunsperse Blue BHD 6000 (Sun Chemicals), Irgalite Blue BCA(Ciba-Geigy), Paliogen Blue 6470 (BASF), Sudan III (Matheson, Coleman,Bell), Sudan II (Matheson, Coleman, Bell), Sudan IV (Matheson, Coleman,Bell), Sudan Orange G (Aldrich), Sudan Orange 220 (BASF), PaliogenOrange 3040 (BASF), Ortho Orange OR 2673 (Paul Uhlich), Paliogen Yellow152, 1560 (BASF), Lithol Fast Yellow 0991K (BASF), Paliotol Yellow 1840(BASF), Neopen Yellow (BASF), Novoperm Yellow FG 1 (Hoechst), PermanentYellow YE 0305 (Paul Uhlich), Lumogen Yellow D0790 (BASF), SunsperseYellow YHD 6001 (Sun Chemicals), Suco-Gelb L1250 (BASF), Suco-YellowD1355 (BASF), Hostaperm Pink E (American Hoechst), Fanal Pink D4830(BASF), Cinquasia Magenta (DuPont), Lithol Scarlet D3700 (BASF),Toluidine Red (Aldrich), Scarlet for Thermoplast NSD PS PA (UgineKuhlmann of Canada), E.D. Toluidine Red (Aldrich), Lithol Rubine Toner(Paul Uhlich), Lithol Scarlet 4440 (BASF), Bon Red C (Dominion ColorCompany), Royal Brilliant Red RD-8192 (Paul Uhlich), Oracet Pink RF(Ciba-Geigy), Paliogen Red 3871K (BASF), Paliogen Red 3340 (BASF),Lithol Fast Scarlet L4300 (BASF), combinations of the foregoing, and thelike.

In embodiments, the colorant may include a pigment, a dye, combinationsthereof, carbon black, magnetite, black, cyan, magenta, yellow, red,green, blue, brown, combinations thereof, in an amount sufficient toimpart the desired color to the toner. It is to be understood that otheruseful colorants will become readily apparent based on the presentdisclosures.

In embodiments, a pigment or colorant may be employed in an amount offrom about 1% by weight to about 35% by weight of the toner particles ona solids basis, in embodiments, from about 5% by weight to about 25% byweight.

Wax

Optionally, a wax may also be combined with the resin and a colorant informing toner particles. The wax may be provided in a wax dispersion,which may include a single type of wax or a mixture of two or moredifferent waxes. A single wax may be added to toner formulations, forexample, to improve particular toner properties, such as toner particleshape, presence and amount of wax on the toner particle surface,charging and/or fusing characteristics, gloss, stripping, offsetproperties, and the like. Alternatively, a combination of waxes can beadded to provide multiple properties to the toner composition.

When included, the wax may be present in an amount of, for example, fromabout 1% by weight to about 25% by weight of the toner particles, inembodiments from about 5% by weight to about 20% by weight of the tonerparticles, although the amount of wax can be outside of these ranges.

When a wax dispersion is used, the wax dispersion may include any of thevarious waxes conventionally used in emulsion aggregation tonercompositions. Waxes that may be selected include waxes having, forexample, an average molecular weight of from about 500 to about 20,000,in embodiments from about 1,000 to about 10,000. Waxes that may be usedinclude, for example, polyolefins such as polyethylene including linearpolyethylene waxes and branched polyethylene waxes, polypropyleneincluding linear polypropylene waxes and branched polypropylene waxes,polyethylene/amide, polyethylenetetrafluoroethylene,polyethylenetetrafluoroethylene/amide, and polybutene waxes such ascommercially available from Allied Chemical and Petrolite Corporation,for example POLYWAX™ polyethylene waxes such as commercially availablefrom Baker Petrolite, wax emulsions available from Michaelman, Inc. andthe Daniels Products Company, EPOLENE N-15™ commercially available fromEastman Chemical Products, Inc., and VISCOL 550-P™, a low weight averagemolecular weight polypropylene available from Sanyo Kasei K. K.;plant-based waxes, such as carnauba wax, rice wax, candelilla wax,sumacs wax, and jojoba oil; animal-based waxes, such as beeswax;mineral-based waxes and petroleum-based waxes, such as montan wax,ozokerite, ceresin, paraffin wax, microcrystalline wax such as waxesderived from distillation of crude oil, silicone waxes, mercapto waxes,polyester waxes, urethane waxes; modified polyolefin waxes (such as acarboxylic acid-terminated polyethylene wax or a carboxylicacid-terminated polypropylene wax); Fischer-Tropsch wax; ester waxesobtained from higher fatty acid and higher alcohol, such as stearylstearate and behenyl behenate; ester waxes obtained from higher fattyacid and monovalent or multivalent lower alcohol, such as butylstearate, propyl oleate, glyceride monostearate, glyceride distearate,and pentaerythritol tetra behenate; ester waxes obtained from higherfatty acid and multivalent alcohol multimers, such as diethyleneglycolmonostearate, dipropyleneglycol distearate, diglyceryl distearate, andtriglyceryl tetrastearate; sorbitan higher fatty acid ester waxes, suchas sorbitan monostearate, and cholesterol higher fatty acid ester waxes,such as cholesteryl stearate. Examples of functionalized waxes that maybe used include, for example, amines, amides, for example AQUA SUPERSLIP6550™, SUPERSLIP 6530™ available from Micro Powder Inc., fluorinatedwaxes, for example POLYFLUO 190™, POLYFLUO 200™, POLYSILK 19™, POLYSILK14™ available from Micro Powder Inc., mixed fluorinated, amide waxes,such as aliphatic polar amide functionalized waxes; aliphatic waxesconsisting of esters of hydroxylated unsaturated fatty acids, forexample MICROSPERSION 19™ also available from Micro Powder Inc., imides,esters, quaternary amines, carboxylic acids or acrylic polymer emulsion,for example JONCRYL 74™, 89™, 130™, 537™, and 538™, all available fromSC Johnson Wax, and chlorinated polypropylenes and polyethylenesavailable from Allied Chemical and Petrolite Corporation and SC Johnsonwax. Mixtures and combinations of the foregoing waxes may also be usedin embodiments. Waxes may be included as, for example, fuser rollrelease agents. In embodiments, the waxes may be crystalline ornon-crystalline.

In embodiments, the wax may be incorporated into the toner in the formof one or more aqueous emulsions or dispersions of solid wax in water,where the solid wax particle size may be of from about 100 nm to about300 nm, in embodiments from about 125 nm to about 275 nm.

Toner Preparation

The toner particles may be prepared by any method within the purview ofone skilled in the art. Although embodiments relating to toner particleproduction are described below with respect to emulsion aggregationprocesses, any suitable method of preparing toner particles may be used,including chemical processes, such as suspension and encapsulationprocesses disclosed in U.S. Pat. Nos. 5,290,654 and 5,302,486, thedisclosures of each of which are hereby incorporated by reference intheir entirety. In embodiments, toner compositions and toner particlesmay be prepared by aggregation and coalescence processes in whichsmall-size resin particles are aggregated to the appropriate tonerparticle size and then coalesced to achieve the final toner particleshape and morphology.

In embodiments, toner compositions may be prepared by emulsionaggregation processes, such as a process that includes aggregating amixture of an optional colorant, an optional wax and any other desiredor required additives, and emulsions including the resins describedabove, optionally in surfactants as described above, and then coalescingthe aggregate mixture. A mixture may be prepared by adding a colorantand optionally a wax or other materials, which may also be optionally ina dispersion(s) including a surfactant, to the emulsion, which may be amixture of two or more emulsions containing the resin. The pH of theresulting mixture may be adjusted by an acid such as, for example,acetic acid, nitric acid or the like. In embodiments, the pH of themixture may be adjusted to from about 2 to about 5. Additionally, inembodiments, the mixture may be homogenized. If the mixture ishomogenized, homogenization may be accomplished by mixing at about 600to about 6,000 revolutions per minute. Homogenization may beaccomplished by any suitable means, including, for example, an IKA ULTRATURRAX T50 probe homogenizer.

Following the preparation of the above mixture, an aggregating agent maybe added to the mixture. Any suitable aggregating agent may be utilizedto form a toner. Suitable aggregating agents include, for example,aqueous solutions of a divalent cation or a multivalent cation material.The aggregating agent may be, for example, an inorganic cationicaggregating agent such as polyaluminum halides such as polyaluminumchloride (PAC), or the corresponding bromide, fluoride, or iodide,polyaluminum silicates such as polyaluminum sulfosilicate (PASS), andwater soluble metal salts including aluminum chloride, aluminum nitrite,aluminum sulfate, potassium aluminum sulfate, calcium acetate, calciumchloride, calcium nitrite, calcium oxylate, calcium sulfate, magnesiumacetate, magnesium nitrate, magnesium sulfate, zinc acetate, zincnitrate, zinc sulfate, zinc chloride, zinc bromide, magnesium bromide,copper chloride, copper sulfate, and combinations thereof. Inembodiments, the aggregating agent may be added to the mixture at atemperature that is below the glass transition temperature (Tg) of theresin.

Suitable examples of organic cationic aggregating agents include, forexample, dialkyl benzenealkyl ammonium chloride, lauryl trimethylammonium chloride, alkylbenzyl methyl ammonium chloride, alkyl benzyldimethyl ammonium bromide, benzalkonium chloride, cetyl pyridiniumbromide, C₁₂, C₁₅, C₁₇ trimethyl ammonium bromides, halide salts ofquaternized polyoxyethylalkylamines, dodecylbenzyl triethyl ammoniumchloride, combinations thereof, and the like.

Other suitable aggregating agents also include, but are not limited to,tetraalkyl titanates, dialkyltin oxide, tetraalkyltin oxide hydroxide,dialkyltin oxide hydroxide, aluminum alkoxides, alkylzinc, dialkyl zinc,zinc oxides, stannous oxide, dibutyltin oxide, dibutyltin oxidehydroxide, tetraalkyl tin, combinations thereof, and the like. Where theaggregating agent is a polyion aggregating agent, the agent may have anydesired number of polyion atoms present. For example, in embodiments,suitable polyaluminum compounds have from about 2 to about 13, inembodiments, from about 3 to about 8, aluminum ions present in thecompound.

The aggregating agent may be added to the mixture utilized to form atoner in an amount of, for example, from about 0% to about 10% byweight, in embodiments from about 0.2% to about 8% by weight, inembodiments from about 0.5% to about 5% by weight, of the resin in themixture. This should provide a sufficient amount of agent foraggregation.

The particles may be permitted to aggregate until a predetermineddesired particle size is obtained. A predetermined desired size refersto the desired particle size to be obtained as determined prior toformation, and the particle size being monitored during the growthprocess until such particle size is reached. Samples may be taken duringthe growth process and analyzed, for example with a Coulter Counter, foraverage particle size. The aggregation thus may proceed by maintainingthe elevated temperature, or slowly raising the temperature to, forexample, from about 40° C. to about 100° C., and holding the mixture atthis temperature for a time of from about 0.5 hours to about 6 hours, inembodiments from about hour 1 to about 5 hours, while maintainingstirring, to provide the aggregated particles. Once the predetermineddesired particle size is reached, then the growth process is halted.

The growth and shaping of the particles following addition of theaggregation agent may be accomplished under any suitable conditions. Forexample, the growth and shaping may be conducted under conditions inwhich aggregation occurs separate from coalescence. For separateaggregation and coalescence stages, the aggregation process may beconducted under shearing conditions at an elevated temperature, forexample of from about 40° C. to about 90° C., in embodiments from about45° C. to about 80° C., which may be below the glass transitiontemperature of the resin as discussed above.

Once the desired final size of the toner particles is achieved, the pHof the mixture may be adjusted with a base to a value of from about 3 toabout 10, and in embodiments from about 5 to about 9. The adjustment ofthe pH may be utilized to freeze, that is to stop, toner growth. Thebase utilized to stop toner growth may include any suitable base suchas, for example, alkali metal hydroxides such as, for example, sodiumhydroxide, potassium hydroxide, ammonium hydroxide, combinationsthereof, and the like. In embodiments, ethylene diamine tetraacetic acid(EDTA) may be added to help adjust the pH to the desired values notedabove.

Shell Resin

In embodiments, after aggregation, but prior to coalescence, a resincoating may be applied to the aggregated particles to form a shellthereover. Any resin described above may be utilized as the shell. Inembodiments, a bio-based polyester amorphous resin latex as describedabove may be included in the shell. In yet embodiments, the polyesteramorphous resin latex described above may be combined with a differentresin, and then added to the particles as a resin coating to form ashell.

Multiple resins may be utilized in any suitable amounts. In embodiments,a first amorphous polyester resin, for example a bio-based amorphousresin described above, may be present in an amount of from about 20percent by weight to about 100 percent by weight of the total shellresin, in embodiments from about 30 percent by weight to about 90percent by weight of the total shell resin. Thus, in embodiments, asecond resin may be present in the shell resin in an amount of fromabout 0 percent by weight to about 80 percent by weight of the totalshell resin, in embodiments from about 10 percent by weight to about 70percent by weight of the shell resin.

The shell resin may be applied to the aggregated particles by any methodwithin the purview of those skilled in the art. In embodiments, theresins utilized to form the shell may be in an emulsion including anysurfactant described above. The emulsion possessing the resins, may becombined with the aggregated particles described above so that the shellforms over the aggregated particles.

The formation of the shell over the aggregated particles may occur whileheating to a temperature of from about 30° C. to about 80° C., inembodiments from about 35° C. to about 70° C. The formation of the shellmay take place for a period of time of from about 5 minutes to about 10hours, in embodiments from about 10 minutes to about 5 hours.

Coalescence

Following aggregation to the desired particle size and application ofany optional shell, the particles may then be coalesced to the desiredfinal shape, the coalescence being achieved by, for example, heating themixture to a temperature of from about 45° C. to about 100° C., inembodiments from about 55° C. to about 99° C., which may be at or abovethe glass transition temperature of the resins utilized to form thetoner particles, and/or reducing the stirring, for example to from about100 rpm to about 1,000 rpm, in embodiments from about 200 rpm to about800 rpm. Coalescence may occur at a pH of from about 5 to about 8, inembodiments from about 6 to about 7. Coalescence may be accomplishedover a period of from about 0.01 to about 9 hours, in embodiments fromabout 0.1 to about 4 hours.

After aggregation and/or coalescence, the mixture may be cooled to roomtemperature, such as from about 20° C. to about 25° C. The cooling maybe rapid or slow, as desired. A suitable cooling method may includeintroducing cold water to a jacket around the reactor. After cooling,the toner particles may be optionally washed with water, and then dried.Drying may be accomplished by any suitable method for drying including,for example, freeze-drying.

Additives

In embodiments, the toner particles may also contain other optionaladditives, as desired or required. For example, the toner may includepositive or negative charge control agents, for example in an amount offrom about 0.1 to about 10% by weight of the toner, in embodiments fromabout 1 to about 3% by weight of the toner. Examples of suitable chargecontrol agents include quaternary ammonium compounds inclusive of alkylpyridinium halides; bisulfates; alkyl pyridinium compounds, includingthose disclosed in U.S. Pat. No. 4,298,672, the disclosure of which ishereby incorporated by reference in its entirety; organic sulfate andsulfonate compositions, including those disclosed in U.S. Pat. No.4,338,390, the disclosure of which is hereby incorporated by referencein its entirety; cetyl pyridinium tetrafluoroborates; distearyl dimethylammonium methyl sulfate; aluminum salts such as BONTRON E84™ or E88™(Orient Chemical Industries, Ltd.); combinations thereof, and the like.

There can also be blended with the toner particles external additiveparticles after formation including flow aid additives, which additivesmay be present on the surface of the toner particles. Examples of theseadditives include metal oxides such as titanium oxide, silicon oxide,aluminum oxides, cerium oxides, tin oxide, mixtures thereof, and thelike; colloidal and amorphous silicas, such as AEROSIL®, metal salts andmetal salts of fatty acids inclusive of zinc stearate, calcium stearate,or long chain alcohols such as UNILIN 700, and mixtures thereof.

In general, silica may be applied to the toner surface for toner flow,triboelectric enhancement, admix control, improved development andtransfer stability, and higher toner blocking temperature. TiO₂ may beapplied for improved relative humidity (RH) stability, triboelectriccontrol and improved development and transfer stability. Zinc stearate,calcium stearate and/or magnesium stearate may optionally also be usedas an external additive for providing lubricating properties, developerconductivity, triboelectric enhancement, enabling higher toner chargeand charge stability by increasing the number of contacts between tonerand carrier particles. In embodiments, a commercially available zincstearate known as Zinc Stearate L, obtained from Ferro Corporation, maybe used. The external surface additives may be used with or without acoating.

Each of these external additives may be present in an amount of fromabout 0.1% by weight to about 5% by weight of the toner, in embodimentsof from about 0.25% by weight to about 3% by weight of the toner,although the amount of additives can be outside of these ranges. Inembodiments, the toners may include, for example, from about 0.1% byweight to about 5% by weight titania, from about 0.1% by weight to about8% by weight silica, and from about 0.1% by weight to about 4% by weightzinc stearate.

Suitable additives include those disclosed in U.S. Pat. Nos. 3,590,000and 6,214,507, the disclosures of each of which are hereby incorporatedby reference in their entirety.

The following Examples are being submitted to illustrate embodiments ofthe present disclosure. These Examples are intended to be illustrativeonly and are not intended to limit the scope of the present disclosure.

EXAMPLES Example 1

Emulsification of BIOREZ™ AIR-64-116 with sodium dodecylbenzenesulfonate (SDBS) and NaOH via extrusion process.

About 88 grams of BIOREZ™ AIR-64-116 resin (commercially available fromAdvanced Image Resources), about 13.2 grams of SDBS, and about 1.76grams of ground NaOH powder were measured into a 250 ml plastic beaker.The mixture was mixed with a spatula for about two minutes. This mixturewas fed into an extruder (a Leistritz MICRO 18 extruder) at a rate ofabout 16.7 grams/minute. The extruder was operated at a screw speed ofabout 120 rpm and with a specified barrel temperature profile of(cooling/130° C./130° C./130° C./125° C./99° C./99° C./99° C./99° C.)over its 8 sections plus a die plate. As the material traveled down thescrew and melted, pre-heated de-ionized water was injected into theextruder at rate of about 15 grams/minute at the sixth port. The productfrom the extruder included a stream of latex that was collected anddiluted with a fixed amount of de-ionized water in a small beaker withgentle agitation.

The particle size distribution for the latex produced is shown in FIG.2.

Example 2

Emulsification of BIOREZ™ AIR-64-116 with SDBS and piperazine viaextrusion process

About 120 grams of the BIOREZ™ AIR-64-116 resin described in Example 1above, about 18 grams of SDBS, and about 2.4 grams of ground piperazinepowder were measured into a 500 ml plastic beaker. The mixture was mixedwith a spatula for about two minutes. This mixture was fed into theextruder described in Example 1 above at a rate of about 16.7grams/minute. The extruder was operated at a screw speed of about 120rpm and with a specified barrel temperature profile (cooling/130°C./140° C./140° C./140° C./99° C./99° C./99° C./99° C.) over its 8sections plus a die plate. As the material traveled down the screw andmelted, pre-heated de-ionized water was injected into the extruder atrate of about 15 grams/minute at the sixth port. The product from theextruder included a stream of latex that was collected and diluted witha fixed amount of deionized water in a small beaker with gentleagitation. The particle size distribution for the latex produced isshown in FIG. 3.

Example 3

Emulsification of BIOREZ™ AIR-64-116 with sodium lauryl sulfate (SLS)and NaOH via extrusion process.

About 120 grams of the BIOREZ™ AIR-64-116 resin described in Example 1,about 18 grams of SLS, and about 2.4 grams of ground NaOH powder weremeasured into a 500 ml plastic beaker. The mixture was mixed with aspatula for about two minutes. This mixture was fed into the extruderdescribed in Example 1 at a rate of about 16.7 grams/minute. Theextruder was operated at a screw speed of about 120 rpm and with aspecified barrel temperature profile (cooling/130° C./140° C./140°C./135° C./109° C./109° C./109° C./109° C.) over its 8 sections plus adie plate. As the material traveled down the screw and melted,pre-heated de-ionized water was injected into the extruder at rate ofabout 15 grams/minute at the sixth port. The product from the extruderincluded a stream of latex that was collected and diluted with a fixedamount of deionized water in a small beaker with gentle agitation. Theparticle size distribution for the latex produced is shown in FIG. 4.

Example 4

Emulsification of BIOREZ™ AIR-64-116 with sodium lauryl sulfate (SLS)and piperazine via extrusion process.

About 240 grams of the BIOREZ™ AIR-64-116 resin described above inExample 1, about 36 grams of SLS, and about 4.8 grams of groundpiperazine powder were measured into a 500 ml plastic beaker. Themixture was mixed with a spatula for about two minutes. This mixture wasfed into the extruder described above in Example 1 at a rate of about 25grams/minute. The extruder was operated at a screw speed of about 120rpm and with a specified barrel temperature profile (cooling/130°C./140° C./140° C./135° C./99° C./99° C./99° C./99° C.) over its 8sections plus a die plate. As the material traveled down the screw andmelted, pre-heated de-ionized water was added at the third and sixthports into the extruder at a rate of about 10 grams/minute and about 25grams/minute, respectively. The product from the extruder included astream of latex that was collected and diluted with a fixed amount ofdeionized water in a small beaker with gentle agitation. About 250 gramsof emulsion was generated. The particle size distribution for the latexproduced is shown in FIG. 5.

It will be appreciated that variations of the above-disclosed and otherfeatures and functions, or alternatives thereof, may be desirablycombined into many other different systems or applications. Also thatvarious presently unforeseen or unanticipated alternatives,modifications, variations or improvements therein may be subsequentlymade by those skilled in the art which are also intended to beencompassed by the following claims. Unless specifically recited in aclaim, steps or components of claims should not be implied or importedfrom the specification or any other claims as to any particular order,number, position, size, shape, angle, color, or material.

What is claimed is:
 1. A process comprising: contacting at least onebio-based amorphous polyester resin with an optional plasticizer to forma pre-blend mixture; neutralizing the pre-blend mixture with aneutralizing agent; contacting the pre-blend mixture with a surfactant;melt-mixing the pre-blend mixture; contacting the melt-mixed mixturewith de-ionized water to form an oil in water emulsion possessing alatex; and recovering the latex.
 2. The process according to claim 1,wherein the bio-based polyester resin is derived at least in part from amaterial selected from the group consisting of natural triglyceridevegetable oils, phenolic plant oils, and combinations thereof.
 3. Theprocess according to claim 1, wherein the amorphous bio-based polyesterresin includes components selected from the group consisting of a fattydimer diol, a fatty dimer diacid, D-isosorbide, L-tyrosine, glutamicacid, and combinations thereof.
 4. The process according to claim 1,wherein the amorphous bio-based polyester resin comprises isosorbide and1,4-cyclohexane dicarboxylic acid.
 5. The process according to claim 1,wherein the neutralizing agent comprises a solid neutralizing agentselected from the group consisting of ammonium hydroxide, potassiumhydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate,lithium hydroxide, potassium carbonate, potassium bicarbonate,organoamines, and combinations thereof.
 6. The process according toclaim 1, wherein the surfactant is selected from the group consisting ofsodium dodecylsulfate, sodium dodecylbenzene sulfonate, sodium laurylsulfate, sodium dodecylnaphthalene sulfate, dialkyl benzenealkylsulfates, dialkyl benzenealkyl sulfonates, abitic acid, alkyldiphenyloxide disulfonates, branched sodium dodecyl benzene sulfonates,polyvinyl alcohol, polyacrylic acid, methalose, methyl cellulose, ethylcellulose, propyl cellulose, hydroxylethyl cellulose, carboxy methylcellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether,polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether,polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate,polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether,dialkylphenoxy poly(ethyleneoxy)ethanol, alkylbenzyl dimethyl ammoniumchloride, dialkyl benzenealkyl ammonium chloride, lauryl trimethylammonium chloride, alkylbenzyl methyl ammonium chloride, alkyl benzyldimethyl ammonium bromide, benzalkonium chloride, C12 trimethyl ammoniumbromide, C15 trimethyl ammonium bromide, C17 trimethyl ammonium bromide,dodecylbenzyl triethyl ammonium chloride, cetyl pyridinium bromide, andcombinations thereof, and wherein the surfactant is in an aqueoussolution.
 7. The process according to claim 1, wherein the neutralizingagent is selected from the group consisting of ammonium hydroxide,potassium hydroxide, sodium hydroxide, sodium carbonate, sodiumbicarbonate, lithium hydroxide, potassium carbonate, potassiumbicarbonate, piperazine, tris-hydroxymethyl-aminomethane, andcombinations thereof and is added at a concentration of from about 0.1%by weight to 5% by weight of the at least one polyester resin, andwherein the neutralizing agent raises the pH of the emulsion to fromabout 5 to about
 12. 8. The process according to claim 1, whereinparticles in the latex have a size of from about 60 nm to about 300 nm.9. A process comprising: contacting at least one bio-based amorphouspolyester resin derived at least in part from a material selected fromthe group consisting of natural triglyceride vegetable oils, phenolicplant oils, and combinations thereof, with an optional plasticizer in afirst section of an extruder to form a resin mixture; neutralizing theresin mixture in a second section of the extruder with a neutralizingagent selected from the group consisting of ammonium hydroxide,potassium hydroxide, sodium hydroxide, sodium carbonate, sodiumbicarbonate, lithium hydroxide, potassium carbonate, potassiumbicarbonate, piperazine, tris-hydroxymethyl-aminomethane, andcombinations thereof; contacting the resin mixture with a surfactant inthe extruder; melt-mixing the resin mixture in the extruder; contactingthe melt-mixed mixture with de-ionized water to form an oil in wateremulsion possessing a latex in the extruder; and recovering the latexfrom the extruder.
 10. The process according to claim 9, wherein theamorphous bio-based polyester resin includes components selected fromthe group consisting of a fatty dimer diacid, D-isosorbide, L-tyrosine,glutamic acid, and combinations thereof.
 11. The process according toclaim 9, wherein the amorphous bio-based polyester resin comprisesisosorbide and 1,4-cyclohexane dicarboxylic acid.
 12. The processaccording to claim 9, wherein the surfactant is selected from the groupconsisting of sodium dodecylsulfate, sodium dodecylbenzene sulfonate,sodium lauryl sulfate, sodium dodecylnaphthalene sulfate, dialkylbenzenealkyl sulfates, dialkyl benzenealkyl sulfonates, abitic acid,alkyl diphenyloxide disulfonates, branched sodium dodecyl benzenesulfonates, polyvinyl alcohol, polyacrylic acid, methalose, methylcellulose, ethyl cellulose, propyl cellulose, hydroxylethyl cellulose,carboxy methyl cellulose, polyoxyethylene cetyl ether, polyoxyethylenelauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenylether, polyoxyethylene oleyl ether, polyoxyethylene sorbitanmonolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenylether, dialkylphenoxy poly(ethyleneoxy)ethanol, alkylbenzyl dimethylammonium chloride, dialkyl benzenealkyl ammonium chloride, lauryltrimethyl ammonium chloride, alkylbenzyl methyl ammonium chloride, alkylbenzyl dimethyl ammonium bromide, benzalkonium chloride, C12 trimethylammonium bromide, C15 trimethyl ammonium bromide, C17 trimethyl ammoniumbromide, dodecylbenzyl triethyl ammonium chloride, cetyl pyridiniumbromide, and combinations thereof, and wherein the surfactant is in anaqueous solution.
 13. The process according to claim 9, whereinparticles in the latex have a size of from about 60 nm to about 300 nm.14. The process according to claim 9, further comprising contacting thelatex with an optional crystalline resin, a colorant, and an optionalwax to form a second mixture; aggregating the mixture to form particles;adjusting the pH of the mixture to from about 3 to about 10 to stopgrowth of the particles; coalescing the particles at a pH from about 5to about 8 to form toner particles; and recovering the toner particles.15. A process comprising: contacting at least one bio-based amorphouspolyester resin with an optional plasticizer to form a pre-blendmixture; neutralizing the pre-blend mixture with a neutralizing agent;contacting the pre-blend mixture with a surfactant; melt-mixing thepre-blend mixture; contacting the melt-mixed mixture with water to forman oil in water emulsion possessing a latex, contacting the latex withan optional crystalline resin, an optional colorant, and an optional waxto form a second mixture; aggregating the mixture to form particles;adjusting the pH of the mixture to from about 3 to about 10 to stopgrowth of the particles; coalescing the particles at a pH of from about5 to about 8 to form toner particles; and recovering the tonerparticles, and wherein the bio-based polyester resin is derived at leastin part from a material selected from the group consisting of naturaltriglyceride vegetable oils, phenolic plant oils, and combinationsthereof.
 16. The process according to claim 15, wherein the neutralizingagent is selected from the group consisting of ammonium hydroxide,potassium hydroxide, sodium hydroxide, sodium carbonate, sodiumbicarbonate, lithium hydroxide, potassium carbonate, piperazine,tris-hydroxymethyl-aminomethane, and combinations thereof.
 17. Theprocess according to claim 15, wherein said optional crystalline resinis present and said optional colorant is present, and wherein saidcrystalline is a polyester resin.
 18. The process according to claim 15,wherein said optional crystalline polyester and said optional wax arepresent, and wherein said crystalline is a polyester resin.
 19. Theprocess according to claim 15, wherein said optional crystallinepolyester is present, said optional plasticizer is present, and whereinsaid crystalline is a polyester resin.
 20. The process according toclaim 15, wherein said optional crystalline resin is present, saidcolorant is present, said wax is present, and said plasticizer ispresent, and wherein said crystalline is a polyester resin.